JPS62191469A - Carbon, graphite material using thermosetable resin and manufacture - Google Patents
Carbon, graphite material using thermosetable resin and manufactureInfo
- Publication number
- JPS62191469A JPS62191469A JP61034761A JP3476186A JPS62191469A JP S62191469 A JPS62191469 A JP S62191469A JP 61034761 A JP61034761 A JP 61034761A JP 3476186 A JP3476186 A JP 3476186A JP S62191469 A JPS62191469 A JP S62191469A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- graphite material
- group
- producing
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 77
- 229910052799 carbon Inorganic materials 0.000 title claims description 64
- 239000007770 graphite material Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000011347 resin Substances 0.000 title description 21
- 229920005989 resin Polymers 0.000 title description 21
- 239000003575 carbonaceous material Substances 0.000 claims description 50
- 229920001187 thermosetting polymer Polymers 0.000 claims description 48
- 239000011342 resin composition Substances 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- -1 polycyclic aromatic compound Chemical class 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- 239000003377 acid catalyst Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 18
- 239000012756 surface treatment agent Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000004970 halomethyl group Chemical group 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000004593 Epoxy Chemical group 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000686 lactone group Chemical group 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920001059 synthetic polymer Polymers 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 description 18
- 239000011295 pitch Substances 0.000 description 17
- 238000003763 carbonization Methods 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000005087 graphitization Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000007849 furan resin Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- XNKFCDGEFCOQOM-UHFFFAOYSA-N 1,2-dinitronaphthalene Chemical compound C1=CC=CC2=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C21 XNKFCDGEFCOQOM-UHFFFAOYSA-N 0.000 description 2
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 2
- BHCGGVIVFXWATI-UHFFFAOYSA-N 1-[4-(1-hydroxyethyl)phenyl]ethanol Chemical compound CC(O)C1=CC=C(C(C)O)C=C1 BHCGGVIVFXWATI-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KDSNMBNNCZRNPP-UHFFFAOYSA-N [5-(hydroxymethyl)-2,4-dimethylphenyl]methanol Chemical compound CC1=CC(C)=C(CO)C=C1CO KDSNMBNNCZRNPP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009760 electrical discharge machining Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- XVMNDHURKMLRLE-UHFFFAOYSA-N phenanthrene pyrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 XVMNDHURKMLRLE-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な熱硬化性樹脂を使用した炭素、黒鉛材料
及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a carbon and graphite material using a novel thermosetting resin and a method for producing the same.
（従来技術）
従来、炭素、黒鉛材料は、フェノール樹脂、フラン樹脂
、これらの変性物等の熱硬化性樹脂なバインダーあるい
は含浸剤として用いた前駆体を焼成（黒鉛化を含む）し
たり、また、熱硬化性樹脂ではないが石炭系もしくは石
油系の重質油、タール、ピッチ等をバインダーあるいは
含浸剤として用い、これを酸化剤等により不融化（実質
的熱硬化性化）した前駆体を焼成（黒鉛化を含む）する
ことにより得られることが知られている。さらに、一度
焼成した炭素材料にフェノール樹脂、フラン樹脂、ピッ
チ等を含浸剤として含侵し高密度化、高強度化をはかる
技術が知られている。(Prior art) Conventionally, carbon and graphite materials have been produced by firing (including graphitization) precursors used as binders or impregnating agents such as thermosetting resins such as phenolic resins, furan resins, and modified products thereof. Although it is not a thermosetting resin, it is a precursor made by using coal-based or petroleum-based heavy oil, tar, pitch, etc. as a binder or impregnating agent, and making it infusible (substantially thermosetting) with an oxidizing agent. It is known that it can be obtained by firing (including graphitization). Furthermore, a technique is known in which a fired carbon material is impregnated with phenol resin, furan resin, pitch, etc. as an impregnating agent to increase density and strength.
これらのうち、フェノール樹脂、フラン樹脂等の熱硬化
性樹脂をバインダーとする炭素、黒鉛＋ｉｒｉ駆体ある
いはこれを炭化した炭素材に繰返しフェノール樹脂な含
浸、焼成することにより炭素、黒鉛材料の密度や不浸透
性を高め得ることが特開昭５３−３７７１３号公報に開
示されている。また、タール、ピッチ等をバインダーと
して成る炭素、黒鉛前駆体にジニトロナフタレン等の芳
香族ニトロ化合物を添加剤として加えることにより不融
化を促進し、前駆体の炭化収率な高め得ることが特公昭
５３−３５７９２号及び特開昭５２−３１９９６号公報
に開示されている。さらに、タール、ピッチ等をバイン
ダーとして成る炭素、黒鉛前駆体を空気中で加熱処理す
ることにより不融化する方法が特開昭５６−１３４５０
７号公報に開示されている。また、炭酸カルシウム、及
び重炭酸ナトリウムを添加剤として加えることにより、
タール、ピッチの流動を阻止し、モザイク化させること
が特公昭５３−３５７９３号公報に開示されている。Among these, carbon and graphite + iri precursors using thermosetting resins such as phenol resins and furan resins as binders or carbonized carbon materials are repeatedly impregnated with phenol resin and fired to reduce the density of carbon and graphite materials. JP-A-53-37713 discloses that impermeability can be improved. Furthermore, by adding an aromatic nitro compound such as dinitronaphthalene as an additive to a carbon or graphite precursor made of tar, pitch, etc. as a binder, it is possible to promote infusibility and increase the carbonization yield of the precursor. It is disclosed in No. 53-35792 and Japanese Unexamined Patent Publication No. 52-31996. Furthermore, a method of making carbon and graphite precursors made of carbon and graphite precursors using tar, pitch, etc. as a binder by heat treatment in air was disclosed in Japanese Patent Application Laid-Open No. 56-13450.
It is disclosed in Publication No. 7. In addition, by adding calcium carbonate and sodium bicarbonate as additives,
Japanese Patent Publication No. 53-35793 discloses preventing the flow of tar and pitch and forming a mosaic.
また、これら従来の炭素、黒鉛材料は、骨材とバインダ
ーあるいは含浸剤との結合は物理的接着に依存している
。Furthermore, these conventional carbon and graphite materials rely on physical adhesion to bond the aggregate and the binder or impregnant.
（発明か解決しようとする問題点）
ところて、バインターあるいは含浸剤に熱硬化性樹脂を
使用することは、成形、焼成工程を容易なものにてき、
そのコストを低減させるために有効な手段である。(Problem to be solved by the invention) However, the use of thermosetting resin as a binder or impregnation agent facilitates the molding and firing process.
This is an effective means for reducing the cost.
しかしながら、フェノール樹脂、或いはフラン樹脂等の
熱硬化性樹脂をバインダーあるいは含浸剤として用いた
場合には、以後の焼成、黒鉛化後に現われる物理的な性
質が著しく制限される欠点、すなわち、これらの樹脂か
ら得られる炭素、黒鉛質にあっては、極めて黒鉛化性の
低い炭素、黒鉛材料しか得られず、又、炭化収率が低い
ことより、何度も含浸する等の製造上の欠点を有してい
た。However, when thermosetting resins such as phenolic resins or furan resins are used as binders or impregnating agents, there is a drawback that the physical properties that appear after subsequent firing and graphitization are significantly limited. Carbon and graphite materials obtained from carbon and graphite materials have extremely low graphitizability, and due to the low carbonization yield, there are manufacturing disadvantages such as repeated impregnation. Was.
また、バインダーにタール、ピッチ等を使用する際に不
融化を促進する添加剤としてジニトロナフタレン等の芳
香族ニトロ化合物を用いる場合においては炭化収率の向
上等の利点はあるものの、有毒ガスを発生したり、焼成
、黒鉛化後の材質が、難黒鉛化性化してしまうという欠
点を有していた。Furthermore, when using tar, pitch, etc. as a binder, aromatic nitro compounds such as dinitronaphthalene are used as additives to promote infusibility, and although this has the advantage of improving carbonization yield, it also generates toxic gas. However, after firing and graphitizing, the material has the disadvantage that it becomes difficult to graphitize.
さらに、タール、ピッチ等をバインダーとして使用する
場合には、イオウ、酸素などの酸化剤による不融化が必
要であり、この不融化、すなわち実質的な熱硬化性化を
行なわない場合には、焼成過程において成形体に変形が
起こったり、重力方向へのピッチの移動にともなう特性
の不均一性はさけられず、炭化収率の向上も望めないこ
とがら含浸処理をくり返す等の欠点を右していた。この
ため不融化処理か必要となるか、不融化を行なうことに
よって、ピッチ等の本来の黒鉛化性か著しくそこなわれ
、難黒鉛化性の炭素、黒鉛材料しか得られないという欠
点を有していた。Furthermore, when using tar, pitch, etc. as a binder, it is necessary to make it infusible with an oxidizing agent such as sulfur or oxygen. Deformation of the compact occurs during the process, non-uniformity of properties due to pitch movement in the direction of gravity cannot be avoided, and improvements in carbonization yield cannot be expected, which leads to disadvantages such as repeated impregnation treatments. was. For this reason, an infusibility treatment is required, or the infusibility treatment significantly impairs the original graphitizability of pitch, etc., resulting in the disadvantage that only carbon and graphite materials that are difficult to graphitize can be obtained. was.
また、従来の多くの炭素、黒鉛材料の前駆体においＣは
、骨材とバインダーとの結合か物理的接着（アンカー効
果）に依存していることがら、これを焼成、黒鉛化する
ことによって得られる１に素、黒鉛材料には強度的な限
界かあった。In addition, C in many conventional precursors of carbon and graphite materials relies on the bond between aggregate and binder or physical adhesion (anchor effect), so it can be obtained by firing and graphitizing it. First, graphite materials had some strength limitations.
本発明はこのような！バ情に鑑みなされたちのてあり、
本来熱硬化性でありながら炭化収率か高く、寸法収縮か
小さく、黒鉛化性を自由に制御することができ、また従
来のタール、ピッチ等をバインダーとした場合の不均一
性の問題を解消することができ、しかも各種成形方法を
適用することができ、さらに結合強度の優れた炭素、黒
鉛材料及びその製造方法を提供しようとするものである
。This invention is like this! Due to personal circumstances, I am sorry for the inconvenience.
Although it is thermosetting in nature, it has a high carbonization yield, small dimensional shrinkage, and graphitization can be freely controlled, and also solves the problem of non-uniformity when using conventional tar, pitch, etc. as a binder. It is an object of the present invention to provide carbon and graphite materials that can be formed by various molding methods, and that have excellent bonding strength, as well as a method for producing the same.
（問題点を解決するための手段及び作用）すなわち、第
一の発明は、主として二日以上の縮合多環芳香族化合物
と、ヒドロキシメチル基、へロメチル基のいずれか少な
くとも一種の基を二個以−ヒ有するー・環または二日以
上の芳香環から成る芳香族架橋剤と、酸触媒とが反応し
て成る熱硬化性樹脂組成物と二表面官能基を有する骨材
とが：骨材と熱硬化性樹脂組成物との界面において、前
記芳香族架橋剤を主体とする表面処理剤もしくは添加剤
を介し化学的に結合させた後、焼成されて成る炭素、黒
鉛材料であり、また第二、第三の発明は、前記骨材と熱
硬化性樹脂組成物とをその界面において芳香族架橋剤を
主体とする表面処理剤もしくは添加剤を介して化学的に
結合させた後、焼成する前記炭素、黒鉛材料の製造方法
てあり、熱硬化性樹脂組成物と骨材とは焼成過程におい
て一体化して炭化し、前記縮合多環芳香族化合物の種類
を変えることにより、あるいは前記芳香族架橋剤及び前
記酸触媒のりな変えることにより。(Means and effects for solving the problem) That is, the first invention mainly consists of a condensed polycyclic aromatic compound of two days or more and two groups of at least one of a hydroxymethyl group and a heromethyl group. A thermosetting resin composition formed by reacting an aromatic crosslinking agent consisting of a ring or an aromatic ring of two or more days with an acid catalyst, and an aggregate having two surface functional groups: Bone A carbon or graphite material formed by chemically bonding the material and the thermosetting resin composition via a surface treatment agent or additive mainly containing the aromatic crosslinking agent, and then firing the material. The second and third inventions are characterized in that the aggregate and the thermosetting resin composition are chemically bonded at the interface thereof via a surface treatment agent or additive mainly composed of an aromatic crosslinking agent, and then baked. The thermosetting resin composition and the aggregate are integrated and carbonized in the firing process, and the type of the condensed polycyclic aromatic compound is changed, or the aromatic By varying the crosslinking agent and the acid catalyst.
焼成（黒鉛化を含む）後の黒鉛化性を制御することがて
き、しかも結合強度に優れた炭素、黒鉛材料及びその製
造方法を提供するものである。The present invention provides carbon and graphite materials that can control graphitization after firing (including graphitization) and have excellent bonding strength, and a method for producing the same.
以下、この炭素、黒鉛材料について、熱硬化性樹脂組成
物を構成する縮合多環芳香族化合物、芳香族架橋剤、及
び酸触媒と、表面処理剤及び添加剤、さらに骨材につい
て説明する。Hereinafter, regarding this carbon and graphite material, the condensed polycyclic aromatic compound, aromatic crosslinking agent, acid catalyst, surface treatment agent and additives, and aggregate that constitute the thermosetting resin composition will be explained.
縮合多環芳香族化合物には、石炭系若しくは石油系の重
質油、タール、ピッチ、あるいはナフタレン、アントラ
セン、フェナントレン、ピレン。Condensed polycyclic aromatic compounds include coal-based or petroleum-based heavy oil, tar, pitch, or naphthalene, anthracene, phenanthrene, and pyrene.
クリセン、ナフタセン、アセナフテン、アセナフチレン
、ペリレン、コロネン及びこれらを主骨格とする誘導体
の中から選ばれる一種又は二種以上の混合物等を使用す
ることがてきる。One or a mixture of two or more selected from chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as main skeletons can be used.
芳香族架橋剤には、ヒドロキシメチル基、へロメチル基
のいずれか少なくとも一種の基を二個以上有する一環ま
たは二環以丘の芳香環から成る芳香族化合物１例えばｐ
−キシリレンジクロライド、ｐ−キシリレングリコール
（ｌ、４−ヘンゼンジメタノール）、ジメチル−ｐ−キ
シリレングリコール、ジメチル−ｍ−キシリレングリコ
ール等を使用することができる。The aromatic crosslinking agent includes an aromatic compound consisting of a one- or two-ring aromatic ring having two or more of at least one of hydroxymethyl group and heromethyl group.
-xylylene dichloride, p-xylylene glycol (1,4-henzendimethanol), dimethyl-p-xylylene glycol, dimethyl-m-xylylene glycol, etc. can be used.
酸触媒には、塩化アルミニウム、弗化ホウ素等のルイス
酸或いは、硫酸、リン酸、有機スルホン酸、カルボン醸
等のプロトン酸、及びこれらの誘導体の中から選ばれる
一種又は二種以五の混合物を使用することがてきるつ
本発明にあっては、前記縮合多環芳香族化合物のうち分
子量か比較的小さいもの、或いは前記縮合多環芳香族化
合物の誘導体であって分子内に酸素、イオウ等の異種元
素を含むもの、或いは硬化後の熱硬化性樹脂組成物の架
橋密度か高いものを使用する場合には難黒鉛化性の炭素
、黒鉛化質が得られる。又、分子量か比較的大きく、か
つ分子内に酸素、イオウ等の異種元素を含まない原料を
選釈する場合、或いは硬化後の熱硬化性樹脂組成物の１
！橘密度か低い場合には、きわめて黒鉛化性の良好な炭
素、黒鉛化質を得ることができる。The acid catalyst is one selected from Lewis acids such as aluminum chloride and boron fluoride, protonic acids such as sulfuric acid, phosphoric acid, organic sulfonic acids, and carboxyl acids, and one or a mixture of two or more of these derivatives. In the present invention, it is preferable to use a compound having a relatively small molecular weight among the fused polycyclic aromatic compounds, or a derivative of the fused polycyclic aromatic compound containing oxygen or sulfur in the molecule. When using a thermosetting resin composition containing different elements such as, or a thermosetting resin composition having a high crosslinking density after curing, a non-graphitizable carbon or a graphitizable substance can be obtained. In addition, when selecting a raw material that has a relatively large molecular weight and does not contain foreign elements such as oxygen and sulfur in the molecule, or when selecting a raw material that has a relatively large molecular weight and does not contain foreign elements such as oxygen or sulfur,
! When the carbon density is low, carbon with extremely good graphitizability and graphitizable substances can be obtained.
つまり、熱硬化性樹脂組成物を構成する縮合多環芳香族
化合物に分子量が比較的小さいもの、或いは縮合多環芳
香族化合物の誘導体であって分子内に酸素、イオウ等の
異種元素を含むものを使用した場合には、硬化或いは炭
化過程において本発明の架橋剤に由来する架橋の他、分
子内に存在す、る酸素、イオウに起因するランタムな架
橋が起こり、得られる炭素、黒鉛前駆体の架橋密度は著
しく高くなる。従ってこれを焼成、黒鉛化することによ
って乱層構造の発達した不浸透性等の特徴を有する難黒
鉛化性の炭素、黒鉛材料を得ることが可能となる。一方
、熱硬化性樹脂組成物を構成する縮合多環芳香族化合物
にメソフェースピッチ、ドーマントメソフェースピッチ
等のような巨大分子を含むものを使用した場合には、本
発明の架橋剤によって架橋が進行しさらに巨大な分子と
なっても、本来、芳香族分子がもっている黒鉛化性を損
なうことなく易黒鉛化性でしかも炭化収率な向上させた
炭素、黒鉛材料を得ることが可婆となる。これは前記＃
Ｉ硬化性樹脂組成物について先に出願した特願昭６０−
２７８８００号願書に添付した明細書に記載されている
ように、この熱硬化性組成物は芳香族共役系に由来する
導電性を有しており、このことは炭素、黒鉛前駆体中で
芳香族架橋剤と縮合多環芳香族化合物とが同一平面内で
架橋結合し、巨大分子化している、すなわち、極めて黒
鉛結晶にこい配列を示しているため焼成、黒鉛化によっ
て容易に発達した黒鉛結晶が得られると推考されるから
である。In other words, the fused polycyclic aromatic compound constituting the thermosetting resin composition has a relatively small molecular weight, or the derivative of the fused polycyclic aromatic compound contains different elements such as oxygen and sulfur in the molecule. When using carbon, in addition to crosslinking originating from the crosslinking agent of the present invention during the curing or carbonization process, random crosslinking occurs due to oxygen and sulfur present in the molecule, resulting in carbon and graphite precursors. The crosslinking density of is significantly higher. Therefore, by firing and graphitizing this material, it is possible to obtain a non-graphitizable carbon or graphite material which has a developed turbostratic structure and has characteristics such as impermeability. On the other hand, when the fused polycyclic aromatic compound constituting the thermosetting resin composition contains macromolecules such as mesophase pitch, dormant mesophase pitch, etc., the crosslinking agent of the present invention can cause crosslinking. Even if the molecules progress and become even larger, it is possible to obtain carbon and graphite materials that are easily graphitizable and have improved carbonization yields without impairing the graphitizability that aromatic molecules originally have. Become. This is the # above
Patent application filed earlier in 1980 regarding I-curable resin composition
As described in the specification attached to application No. 278800, this thermosetting composition has electrical conductivity derived from an aromatic conjugated system, which means that the aromatic The crosslinking agent and the condensed polycyclic aromatic compound are crosslinked in the same plane, forming a macromolecule. In other words, the graphite crystal is easily developed by firing and graphitization because it shows an arrangement that is extremely similar to graphite crystals. This is because it is presumed that it can be obtained.
これによって、得られた炭素、黒鉛前駆体を焼成、黒鉛
化することにより耐熱性、強度、靭性、弾性、耐摩耗性
、熱伝導性、導電性に優れた炭素、黒鉛材料を得ること
ができる。By firing and graphitizing the obtained carbon and graphite precursors, carbon and graphite materials with excellent heat resistance, strength, toughness, elasticity, abrasion resistance, thermal conductivity, and electrical conductivity can be obtained. .
なお、前記縮合多環芳香族化合物、芳香族架橋剤、及び
酸触媒を反応させて成る熱硬化性組ｌ１ｉＩ２．物とす
るための混合比率については、架橋剤／縮合多環芳香族
＝０．５〜４．０（モル比）の範囲；酸触媒添加量につ
いては、架橋剤／′縮合多環芳香族の混合物に対して０
．５〜１０ｗｔ％か好適な５範囲である。In addition, a thermosetting set l1iI2. formed by reacting the fused polycyclic aromatic compound, an aromatic crosslinking agent, and an acid catalyst. Regarding the mixing ratio for making a product, the range of crosslinking agent / fused polycyclic aromatic = 0.5 to 4.0 (molar ratio); regarding the amount of acid catalyst added, the range of crosslinking agent / 'fused polycyclic aromatic 0 for the mixture
．． The preferred range is 5 to 10 wt%.
また、前記熱硬化性組成物を加熱反応させてなる実質的
に熱可塑性を有する８硬化性中間反応生成物（Ｂステー
ジ樹脂）を得るための反応温度範囲については、６０〜
３００℃か好適な範囲である。Further, the reaction temperature range for obtaining a substantially thermoplastic 8-curing intermediate reaction product (B-stage resin) obtained by subjecting the thermosetting composition to a heating reaction is from 60 to
A suitable range is 300°C.
次に、本発明における表面処理剤及び添加剤については
、前記芳香族架橋剤、若しくは前記芳香族架橋剤と前記
酸触媒との混合物であり、この混合物の融点以１−の温
度に加熱溶融させ液状とし。Next, the surface treatment agent and additive in the present invention are the aromatic crosslinking agent, or a mixture of the aromatic crosslinking agent and the acid catalyst, and are heated and melted at a temperature of 1-1 or higher than the melting point of this mixture. Make it liquid.
若しくは溶剤に溶解させ溶液として骨材の表面処理に使
用する場合、または、添加剤として骨材に添加して使用
する場合も含まれる。また、表面処理剤或いは添加剤の
骨材に対する添加φは特に限定されるものではないが、
０．０１〜５ｗｔ％の範囲か好適である。Alternatively, it also includes cases where it is dissolved in a solvent and used as a solution for surface treatment of aggregates, or cases where it is added to aggregates as an additive. In addition, the addition φ of the surface treatment agent or additive to the aggregate is not particularly limited, but
A range of 0.01 to 5 wt% is suitable.
本発明では骨材として、水素、ハロゲン、ヒドロキシル
基、カルボニル基、カルボキシル基、アルデヒド基、エ
ポキシ構造、ラクトン構造、エーテル構造、酸無水物構
造の中から選ばれる少なくとも一種又は二種以北の表面
官能基を有する、炭素、黒鉛、天然及び合成高分子、及
びこれらの前駆体を使用することがてきる。これらは、
例えば石油系あるいは石炭系生コークス、カルサインコ
ークス、カーボンファーｒバー、人造黒鉛、天然黒鉛、
カーボンブラック、木炭、メソカーボンマイクロビーズ
、バルクメソフェース、硬化させたフェノール、フラン
等の熱硬化性樹脂及びこれらの炭化物である。またその
形態としては、連続Ｗ＆維状、短ｉａ維状１粒状、平状
、塊状、多孔体状、織布状、不織布状等がある。In the present invention, the surface of the aggregate is at least one or two selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure. Carbon, graphite, natural and synthetic polymers, and precursors thereof, having functional groups can be used. these are,
For example, petroleum-based or coal-based raw coke, calcine coke, carbon fiber, artificial graphite, natural graphite,
These include thermosetting resins such as carbon black, charcoal, mesocarbon microbeads, bulk mesoface, hardened phenol, and furan, and their carbides. Further, the forms include continuous W&fiber form, short ia fibrous single grain form, flat form, lump form, porous form, woven fabric form, non-woven fabric form, etc.
骨材の表面官０＠基等については天然及び合成高分子、
炭素前駆体環子めこれらか存在している物はそのまま、
その他の存在していても少量である場合には酸化剤によ
る湿式酸化、及び酸素等による乾式酸化、空気等の酸化
性雰囲気中での粉砕にともなうメカノケミカルな酸化、
或いは水素化等の還元処理による導入か有効である。Natural and synthetic polymers,
These carbon precursor rings are present as they are,
If other substances are present but in small quantities, wet oxidation using an oxidizing agent, dry oxidation using oxygen, etc., mechanochemical oxidation due to crushing in an oxidizing atmosphere such as air,
Alternatively, introduction through reduction treatment such as hydrogenation is effective.
このような表面官衡基を有する骨材と前記熱硬化性樹脂
組成物とは、両者の界面においてヒドロキシメチル基、
ハロメチルノ、（のいずれか少なくとも一種の基を二個
以上有する一環または二日以上の芳香環から成る芳香族
架橋剤、例えばｐ−キシリレンジクロライド、ｐ−キシ
リレングリコール、ジメチル−ｐ−キシリレングリコー
ル等の芳香族架橋剤を主体とする表面処理剤て処理する
か、もしくは添加剤として添加することによって、これ
らの架橋剤を介して化学的に結合している。The aggregate having such a surface equilibrium group and the thermosetting resin composition have hydroxymethyl groups,
An aromatic crosslinking agent consisting of a one- or two- or more-day aromatic ring having two or more of at least one of halomethyl, (), such as p-xylylene dichloride, p-xylylene glycol, dimethyl-p-xylylene glycol They are chemically bonded via these crosslinking agents by treating them with a surface treatment agent that mainly consists of aromatic crosslinking agents, such as, or by adding them as additives.
これによって、骨材と熱硬化性樹脂組成物は炭化、黒鉛
化の過程において、完全に一体化し、従来に例を見ない
結合強度に優れた炭素、黒鉛材料を得ることがてきる。As a result, the aggregate and the thermosetting resin composition are completely integrated during the carbonization and graphitization process, making it possible to obtain a carbon and graphite material with unprecedented bonding strength.
本発明の方法としては、第二の発明の製造方法である予
め骨材表面を表面処理剤によって処理しておく方法、及
び第三の発明の製造方法である添加を熱硬化性樹脂組成
物に添加しておく方法かあり、これらにいずれの方法に
おいても表面処理剤若しくは添加剤をそれらの融点以上
の温度に加熱溶融させ液状とし、若しくは溶剤に溶解さ
せ溶液として使用することができるが、これらのうち骨
材表面を表面処理剤によって予め処理しておく前者の方
法には、溶剤に溶解させ溶液として使用することが好適
である。The method of the present invention includes the method of pre-treating the aggregate surface with a surface treatment agent, which is the manufacturing method of the second invention, and the method of adding to the thermosetting resin composition, which is the manufacturing method of the third invention. In either method, the surface treatment agent or additive can be heated to a temperature higher than its melting point to form a liquid, or it can be dissolved in a solvent and used as a solution. For the former method, in which the surface of the aggregate is pretreated with a surface treatment agent, it is suitable to dissolve it in a solvent and use it as a solution.
本発明によれば、熱硬化性樹脂組成物を：（１）未反応
の粉末混合物として（２）所謂Ｂステージ樹脂の粉末と
して（３）所ｉＢステージ樹脂を加熱溶融させ液状とし
て、あるいは（４）所謂Ｂステージ樹脂を溶剤に溶解さ
せ液状として；バインター、マトリックス、含浸剤、コ
ーティング剤等として使用することができるが、その際
に骨材の形！ムが；連続ｍ＃Ｉ状、織布状、不＃ｌ＆布
状等の場合には（３）または（４）の方法により、含浸
法、フィラメントワインディング法、プレプリング決算
を採用して：単繊維状、粒状、平板状、塊状等の場合に
は（ｉ）または（２）の方法により、混練法、造粒法、
コーティング法等を採用して；ブロック状、多孔体状、
平板状、加工品等の場合には、（３）または（４）の方
法により、含浸法等を採用して：それぞれ複合すること
が好適である。According to the present invention, the thermosetting resin composition is prepared: (1) as an unreacted powder mixture, (2) as a powder of a so-called B-stage resin, (3) as a liquid by heating and melting an iB-stage resin, or (4) as a liquid by heating and melting an iB-stage resin. ) The so-called B-stage resin is dissolved in a solvent and made into a liquid; it can be used as a binder, matrix, impregnating agent, coating agent, etc., but in this case, it is in the form of aggregate! If the fiber is continuous m#I, woven fabric, non-woven fabric, etc., use method (3) or (4), impregnation method, filament winding method, pre-pulling method: monofilament. In the case of shaped, granular, plate-shaped, lump-like, etc., kneading method, granulation method, method (i) or (2) is used.
By adopting coating method etc.; block shape, porous shape,
In the case of a flat plate, a processed product, etc., it is preferable to use the impregnation method or the like according to method (3) or (4) to combine the materials.
また、成形が必要な場合には、ホットプレス、ホットア
イソスタディツクプレス、静水圧プレス、型造、振動、
押し出し、射出、トランスファー、真空、吹きつけ１巻
きつけ、張り合わせ等の内から目的に合う成形上を選択
し、所定の形状に熱硬化成形する。この際、成形温度範
囲は、１００〜４００℃か好適で、複合物か軟化後に熱
硬化するように成形温度及び時間を設定することが肝要
であるゆさらに、後硬化する場合には、後硬化温度は１
００〜４００ ”Ｃが好適な範囲であり、後硬化時間は
１０〜３０時間の範囲が好適である。In addition, if molding is required, hot press, hot isostatic press, isostatic press, molding, vibration,
Select a molding method that suits the purpose from among extrusion, injection, transfer, vacuum, spraying, one-wrap, lamination, etc., and heat-cure it into a predetermined shape. At this time, the molding temperature range is preferably 100 to 400°C, and it is important to set the molding temperature and time so that the composite material is thermally cured after softening. temperature is 1
The preferred range is 00 to 400''C, and the preferred post-curing time is 10 to 30 hours.
焼成は、常法に従って非酸化性雰囲気中でこれを行う。Firing is performed in a non-oxidizing atmosphere according to a conventional method.
特に重質油、タール、ピッチを使用した熱硬化性樹脂組
成物は従来のフェノール、フラン等の熱硬化性樹脂と比
較して遥かに高い炭化率を有しており、このため焼成過
程においては体積収縮か小さく、また従来より速い昇温
速度て焼成でき、サイズも大きなものが得られる。In particular, thermosetting resin compositions using heavy oil, tar, and pitch have a much higher carbonization rate than conventional thermosetting resins such as phenol and furan. It has a small volume shrinkage, can be fired at a faster temperature increase rate than conventional methods, and can be produced in a large size.
また、本発明ては、熱硬化性樹脂組成物自体か硬化した
状態（硬化体）で導電性を示すことがら骨材との複合物
を直接通電したり、誘導加熱することにより焼成するこ
とができる。特に熱硬化性樹脂組成物の縮合多環芳香族
化合物に巨大な共役系縮合多環芳香族分子を含む石炭系
もしくは石油系のタール、ピッチを使用した場合には、
導電性は著しい。In addition, in the present invention, since the thermosetting resin composition itself exhibits conductivity in a cured state (cured product), it is possible to sinter the composite with aggregate by directly applying electricity or by induction heating. can. In particular, when coal-based or petroleum-based tar or pitch containing giant conjugated fused polycyclic aromatic molecules is used as the fused polycyclic aromatic compound of the thermosetting resin composition,
The conductivity is significant.
本発明では、前記直接通電や誘導加熱による他、従来よ
り行なわれている外熱式加熱により焼成することも勿論
でき、各種の炭素、黒鉛材料の製造に応用することが期
待てきる。In addition to the above-mentioned direct current application and induction heating, the present invention can of course be fired by conventional external heating, and is expected to be applied to the production of various carbon and graphite materials.
（実施例） 次に本発明を実施例について更に詳細に説明する。(Example) Next, the present invention will be described in more detail with reference to examples.
実Ｊ４九ユ
市販の粉砕した石油系カルサンコークス（ｆ均粒子径８
０＃Ｌｍ）を空気中４００℃て３時間加熱し、表面に酸
素を含む官能基を導入した後、ｐ−キシリレングリコー
ル： ５ｗｔ％とｐ−トルエンスルホン酸：１ｗｔ％の
エタノール溶液から成る表面処理剤に浸した後、空気中
１２０℃て３０分間熱処理し、これを骨材とした。バイ
ンダーとしては石油系メンフェースピッチ（軟化点２３
０℃）とα−メチルナフタレンを混合（重量比７：３）
し、軟化点を１５０℃に調整したものとジメチル−ｐ−
キシリレングリコールを改Ｍ比て５：２の割合て混合し
、そこに５ ｗ ｔ％のＰ−トルエンスルホン酸を加え
た混合物を１６０℃て１０分間反応させたＢステージ樹
脂を用いた。このＢステージ樹脂と骨材とを重量比てｌ
：２の割合て配合した後、１６０℃、１５分間ニーター
て混練し、混練物を１８０℃てｌＯ１００Ｘ１００ｘ５
０の大きさにホットプレス成形し、硬化させた後、２０
０℃で２０時間後硬化させ、炭素、黒鉛前駆体を得た。Commercially available pulverized petroleum-based Calsan coke (f average particle size 8
0#Lm) was heated in air at 400°C for 3 hours to introduce oxygen-containing functional groups onto the surface, and then the surface was made of an ethanol solution of 5 wt% p-xylylene glycol and 1 wt% p-toluenesulfonic acid. After immersing it in a treatment agent, it was heat-treated in air at 120°C for 30 minutes, and this was used as aggregate. As a binder, petroleum-based menface pitch (softening point 23
0℃) and α-methylnaphthalene (weight ratio 7:3)
and dimethyl-p-
A B-stage resin was used, which was prepared by mixing xylylene glycol at a modified M ratio of 5:2 and reacting the mixture with 5 wt % of P-toluenesulfonic acid at 160° C. for 10 minutes. The weight ratio of this B-stage resin and aggregate is 1
: After blending at a ratio of 2, knead in a kneader at 160°C for 15 minutes, and heat the kneaded material at 180°C to 100 x 100 x 5 lO.
After hot press molding to a size of 0 and hardening, 20
It was post-cured at 0°C for 20 hours to obtain a carbon and graphite precursor.
この前駆体はそれ自体導電性を有するため、非酸化性雰
囲気中、誘導加熱により１５０℃／ ｈ ｒの昇温速度
で２８００℃まて昇温し、２８００℃で１時間保持した
。又、比較のため、この前駆体を非酸化性雰囲気中、直
接通電により４００℃／ ｈ ｒの昇温速度て２８００
℃まで昇温し、２８００℃で１時間保持した。これらの
黒鉛化量の曲げ強度、′１！気比抵抗、ショアー硬度、
見かけ比重を測定したところ、第１表に示すような結果
を得た。Since this precursor itself has conductivity, the temperature was raised to 2800°C at a heating rate of 150°C/hr by induction heating in a non-oxidizing atmosphere, and held at 2800°C for 1 hour. For comparison, this precursor was heated to 2800 °C in a non-oxidizing atmosphere at a heating rate of 400 °C/hr by direct current application.
The temperature was raised to 2800°C and maintained at 2800°C for 1 hour. The bending strength of these graphitized amounts is '1! specific resistance, shore hardness,
When the apparent specific gravity was measured, the results shown in Table 1 were obtained.
第 １ 表
実」１九ユ
水素等の表面官能基を有する石炭系メンカーボンマイク
ロビーズ（平均粒子径５ルｍ）を骨材とし、バインダー
として軟化点８５℃の石炭系ピッチ（平均分子量４００
）と ｐ−キシリレングリコールとをモル比でｌ ：
２．５の割合て混合し、そこに６ ｗ ｔ％の ｐ−ト
ルエンスルホン酸を加えた混合物を用いた。バインダー
組成物に添加剤としてｐ−キシリレンジクロライドを１
．５ｗｔ％添加した後、骨材に対して重量比てｌ：ｌの
割合に配合し、１４０℃で１５分間ヘンシェルミキサー
て骨材にコーティングした。この混練物を押し出し成形
した後、２００℃て硬化させた。その後、硬化物は従来
法に従って焼成し、２８００℃で黒鉛化した。この黒鉛
材料を２０φｘ５０ｍｍの大きさに加工して、放電加工
ａＧ−３０（三菱電気（株）製）に固定して、ＳＫ鋼を
相手材として電極プラス極性で、ケロシン中でピーク１
ｔｆ、ａ ３ Ａ、パルスＩｌｃ！２０ＪＬＳｅＣの条
件で放電加工を行なったつＳＫ鋼を２０φの面積て５ｍ
ｍの深さ加工した後の電極の長さ方向の消耗は、約０．
５ｍｍをきわめて小さい値を示した。Table 1: Coal-based carbon microbeads (average particle size: 5 m) with surface functional groups such as hydrogen are used as aggregates, and coal-based pitch with a softening point of 85°C (average molecular weight: 400 m) is used as a binder.
) and p-xylylene glycol in molar ratio l:
A mixture was used in which 6 wt % of p-toluenesulfonic acid was added thereto. 1 p-xylylene dichloride is added as an additive to the binder composition.
．． After adding 5 wt%, the mixture was blended in a weight ratio of 1:1 to the aggregate, and coated on the aggregate using a Henschel mixer at 140° C. for 15 minutes. This kneaded product was extruded and then cured at 200°C. Thereafter, the cured product was fired according to a conventional method and graphitized at 2800°C. This graphite material was machined to a size of 20φ x 50mm, fixed to electrical discharge machining aG-30 (manufactured by Mitsubishi Electric Co., Ltd.), and with SK steel as a mating material and electrode positive polarity, peak 1 in kerosene.
tf, a 3 A, pulse Ilc! A piece of SK steel that was subjected to electrical discharge machining under the conditions of 20JLSeC was cut into a 20φ area of 5m.
After machining to a depth of m, the wear in the longitudinal direction of the electrode is approximately 0.
It showed an extremely small value of 5 mm.
実施例３
市販の５ｍｍ以下に切断したピッチ系汎用カーボンファ
イバーを空気中４００℃で３時間加熱し、表面に酸素を
含む官能基を導入した後、ｐ−キシリレンジクロライト
： ５ｗｔ％とｐ−トルエンスルホン酸・１ｗｔ％のエ
タノール溶液から成る表面処理剤に浸した後、空気中１
２０℃て３０分間熱処理し、これを骨材とし・た。バイ
ンダーとしては、ピレン−フェナントレンの混合物（モ
ル比７：３）とｐ−キシリレンシクロライトをモル比て
ｌ：１．５の割合で混合し、そこに３ｗｔ％の無水塩化
アルミニウムを加えた混合物を１３０℃で４００分間反
応せたＢステージ樹脂を用いた。Example 3 A commercially available pitch-based general-purpose carbon fiber cut into pieces of 5 mm or less was heated in air at 400°C for 3 hours to introduce oxygen-containing functional groups onto the surface, and then p-xylylene dichlorite: 5 wt% and p- After immersing in a surface treatment agent consisting of toluenesulfonic acid/1 wt% ethanol solution,
It was heat treated at 20°C for 30 minutes and used as aggregate. As the binder, a mixture of pyrene-phenanthrene (molar ratio 7:3) and p-xylylene cyclolite were mixed at a molar ratio of 1:1.5, and 3 wt% of anhydrous aluminum chloride was added thereto. A B-stage resin that was reacted at 130°C for 400 minutes was used.
このＢステージ樹脂を１００ｇｍ以下に粉砕し、骨材と
重量比”Ｃ１： ｌの割合て配合し、充分混合した。混
合物をマイクロ波加熱のモールドブレスを用い１８０℃
で成形し、２００℃でｌ Ｏ１ｔ４ｊ間後硬化させ炭素
、黒鉛前駆体を得た。前駆体を非酸化性雰囲気中２００
℃／ ｈ ｒの昇温速度て２０００℃まで昇温したとこ
ろ、気孔率８０％の多孔質黒鉛材料が得られた。又、こ
の多孔質黒鉛材料は優れた耐熱性と高温断熱特性を示し
た。This B-stage resin was pulverized to 100 gm or less, blended with aggregate at a weight ratio of 1:1, and thoroughly mixed.The mixture was heated at 180°C using a microwave-heated mold press.
The carbon and graphite precursors were obtained by molding and post-curing at 200° C. for 1 O1t4j. Precursor in a non-oxidizing atmosphere
When the temperature was raised to 2000°C at a heating rate of °C/hr, a porous graphite material with a porosity of 80% was obtained. Moreover, this porous graphite material showed excellent heat resistance and high temperature insulation properties.
実施例４
石油系生コークスを超微粉砕機により空気中で１１０１
ｚ以下に粉砕し、粉砕と同時に酸素を含む表面官能基を
導入し、これを骨材とした。バインターとしては、軟化
点１１５℃石女系エアフローピ、ソチ（平均分子早約６
００）とｐ−キシリレンジクロライトをモル比で１：２
の割合で混合し、ここに無水塩化アルミニウムを３ ｗ
ｔ％添加した混合物を１２０℃で１５分間反応させた
Ｂステージ樹１１ｔｉを用いた。このＢステー・ジ樹脂
を４０μｍ以下に粉砕し、これと骨材とを重量・比で２
：１の割合て配合し、添加剤として骨材に対してｐ−キ
シリレンジクロライトを１．０ｗｔ％、ｐ−トルエンス
ルホン酸を１．０ｗｔ％加えた後１８０℃で１００φｘ
ｉｏｔの大きさにインジェクション成形した。続いて２
００℃で１５時間、後硬化し炭素、黒鉛前駆体を得た。Example 4 Petroleum-based raw coke was pulverized in air using an ultrafine mill.
The material was ground to a particle size of z or less, and surface functional groups containing oxygen were introduced at the same time as the grinding, and this was used as aggregate. As a binder, the softening point is 115℃, Ishijoke Airflowpi, Sochi (average molecular
00) and p-xylylene dichlorite in a molar ratio of 1:2.
3 w of anhydrous aluminum chloride.
A B-stage tree 11ti in which a mixture containing t% was reacted at 120° C. for 15 minutes was used. This B-stage resin is crushed to 40 μm or less, and this and aggregate are combined in a weight/ratio of 2
: 1.0 wt% p-xylylene dichlorite and 1.0 wt% p-toluenesulfonic acid were added to the aggregate as additives, and then heated to 100φx at 180°C.
It was injection molded to the size of IoT. followed by 2
Post-curing was carried out at 00° C. for 15 hours to obtain a carbon and graphite precursor.
この前駆体は常法に従い焼成し、２５００ ’Ｃて黒鉛
化した。この黒鉛材料は９ ｋ ｇ ／ ｃ ｒｎ’の
空気に対し不浸透てあった。This precursor was calcined in a conventional manner and graphitized at 2500'C. This graphite material was impermeable to 9 kg/c rn' of air.
実施例５
市販の黒鉛材料（気孔率１６％）を２００ｘ２００Ｘ１
００ｍｍの各ブロックに加工し、ｐ−キシリレンクリコ
ール５ｗｔ％、Ｐ−）−ルエンスルポン酸２ｗｔ％のエ
タノール溶液を減圧含浸した後、１５０℃空気中てｌｈ
ｒ乾燥し、これを骨材とした。含浸剤として、市販の石
炭系含浸用ピッチ（軟化点８５℃，炭化収率５３％、平
均分子量４００）とジメチル−ｍ−キシリレングリコー
ルをモル比てｌ：２て混合し、そこにトリフルオロメタ
ンスルホン酸を５ ｗ ｔ％混合し、１２０℃て４０分
間窒素気流中で反応させたＢステージ樹脂（軟化点７０
℃）を用い、骨材ブロックに１５０℃て減圧含浸した。Example 5 Commercially available graphite material (porosity 16%) 200x200x1
After processing each block into 00 mm blocks and impregnating them with an ethanol solution containing 5 wt% of p-xylylene glycol and 2 wt% of P-)-luenesulfonic acid under reduced pressure, they were heated at 150°C in air for lh.
It was dried and used as aggregate. As an impregnating agent, commercially available coal-based impregnating pitch (softening point 85°C, carbonization yield 53%, average molecular weight 400) and dimethyl-m-xylylene glycol were mixed at a molar ratio of 1:2, and trifluoromethane was added thereto. B-stage resin (softening point: 70
The aggregate block was impregnated under reduced pressure at 150°C.
比較のため含浸用ピッチのみを１５０℃で減圧含浸し、
両者とも５０℃／ ｈ ｒの昇温速度で酸化性雰囲気中
８００℃まて焼成後、常法に従って２８００℃で黒鉛化
した。これらの見かけ比重、電気比抵抗、熱伝導率につ
いての測定結果を第２表に示す。For comparison, only pitch for impregnation was impregnated under reduced pressure at 150°C.
Both were fired to 800°C in an oxidizing atmosphere at a heating rate of 50°C/hr, and then graphitized at 2800°C according to a conventional method. The measurement results of these apparent specific gravity, electrical resistivity, and thermal conductivity are shown in Table 2.
第 ２ 表
（発明の効果〕
以上本発明によれば、その炭素、黒鉛材料は、骨材と熱
硬化性樹脂組成物とがその界面において芳香族架橋剤を
主体とする表面処理剤もしくは添加剤を介し化学的に結
合させた後、焼成して成るちのてあり、熱硬化性樹脂組
成物と骨材とは焼成過程において一体化して炭化し、結
合強度に優れたものとなっている。また、本発明によれ
は、熱硬化性樹脂組成物の縮合多環１香族化合物の種類
を変えることにより、あるいは前記庁香族架橋剤及び前
記酸触媒の量を変え架橋密度を変化させることにより、
焼１ｊｉ、（黒鉛化を含む）後の黒鉛化性を難黒鉛化性
のものから易黒鉛化性のものまて制御することがてきる
。また、本発明に係る炭素、黒鉛材料は熱硬化性樹脂で
ありながら炭化収率が高く、寸法収縮か小さいから、比
較的大きなサイズのものを製造するのにも適している。Table 2 (Effects of the Invention) According to the present invention, the carbon or graphite material is treated with a surface treatment agent or additive mainly containing an aromatic crosslinking agent at the interface between the aggregate and the thermosetting resin composition. The thermosetting resin composition and the aggregate are bonded chemically through a compound and then fired, and the thermosetting resin composition and aggregate are integrated and carbonized during the firing process, resulting in excellent bonding strength. According to the present invention, by changing the type of fused polycyclic monoaromatic compound in the thermosetting resin composition, or by changing the amount of the aromatic crosslinking agent and the acid catalyst and changing the crosslinking density. ,
The graphitizability after firing (including graphitization) can be controlled from non-graphitizable to easily graphitizable. Furthermore, although the carbon and graphite materials according to the present invention are thermosetting resins, they have a high carbonization yield and small dimensional shrinkage, so they are suitable for manufacturing relatively large products.
さらに。moreover.
成形か容易であり、各種の成形方法に適用することがて
きる。It is easy to mold and can be applied to various molding methods.
また、本発明に係る炭素、黒鉛材料を製造する際の焼成
に、熱硬化性樹脂組成物か硬化した状態（硬化体）で導
電性を示すことがら、直接通電したり、誘導加熱するこ
とによる焼成かてき、外熱式加熱による製造に適さない
炭素、黒鉛材料の製造に適している。In addition, since the thermosetting resin composition exhibits conductivity in the cured state (cured material) during firing when producing the carbon and graphite materials according to the present invention, direct current application or induction heating may be used. Suitable for manufacturing carbon and graphite materials that are not suitable for manufacturing by firing or external heating.
この様にして、本発明により、種々の黒鉛化性を示し１
強度、弾性率、摺動特性等の機械的性質、８伝等率、熱
膨張率、耐スポーリンク性等の熱的性質、電気比抵抗等
の電気的性質などの物理的特性を自由に制御しつる炭素
、黒鉛材料を製造し得る。In this way, the present invention exhibits various graphitizability.
Freely control physical properties such as mechanical properties such as strength, elastic modulus, and sliding properties, thermal properties such as 8 conductivity coefficient, thermal expansion coefficient, and anti-spawl link properties, and electrical properties such as electrical resistivity. It can produce solid carbon and graphite materials.
また、製造工程においては熱硬化性の特徴を生かし、種
々の賦形方法か採用てき、かつ、低収縮、高ζを法、安
定性、高炭化率によって、大幅なコスト低減か期待てき
る。In addition, in the manufacturing process, various shaping methods can be used to take advantage of the thermosetting characteristics, and due to low shrinkage, high ζ, stability, and high carbonization rate, it is expected to significantly reduce costs.
手続補正書 （自発） 昭和５２年０２月２０日Procedural amendment (voluntary) February 20, 1978
Claims (1)
ロキシメチル基、ハロメチル基のいずれか少なくとも一
種の基を一個以上有する一環または一環以上の芳香環か
ら成る芳香族架橋剤と、酸触媒とが反応して成る熱硬化
性樹脂組成物と：表面官能基を有する骨材とが：骨材と
熱硬化性樹脂組成物との界面において、前記芳香族架橋
剤を主体とする表面処理剤もしくは添加剤を介し化学的
に結合させた後、焼成されて成ることを特徴とする炭素
、黒鉛材料。 ２）特許請求の範囲第１項記載の炭素、黒鉛材料におい
て、前記熱硬化性樹脂組成物は、前記縮合多環芳香族化
合物と前記芳香族架橋剤と前記酸触媒との混合物、もし
くはこれらの熱硬化性中間反応性成物の中から選ばれる
少なくとも一種が反応により熱硬化されて成ることを特
徴とする炭素、黒鉛材料。 ３）特許請求の範囲第１項記載の炭素、黒鉛材料におい
て、前記縮合多環芳香族化合物は、石炭系もしくは石油
系の重質油、タール、ピッチ、あるいはナフタレン、ア
ントラセン、フェナントレン、ピレン、クリセン、ナフ
タセン、アセナフテン、アセナフチレン、ペリレン、コ
ロネン、及びこれらを主骨格とする誘導体の中から選ば
れる一種又は二種以上の混合物であるこを特徴とする炭
素、黒鉛材料。 ４）特許請求の範囲第１項記載の炭素、黒鉛材料におい
て、前記酸触媒は、塩アルミニウム、弗化ホウ素、リン
酸、有機スルホン酸、カルボン酸、及びこれらの誘導体
の中から選ばれる一種又は二種以上の混合物であること
を特徴とする炭素、黒鉛材料。 ５）特許請求の範囲第１項記載の炭素、黒鉛材料におい
て、前記骨材は、炭素、黒鉛、天然及び合成高分子、及
びこれらの前駆体の中から選ばれる一種又は二種以上の
化合物もしくは混合物であり、少なくともその表面に水
素、ハロゲン、ヒドロキシル基、カルボニル基、カルボ
キシル基、アルデヒド基、エポキシ構造、ラクトン構造
、エーテル構造、酸無水物構造の中から選ばれる一種又
は二種以上を予め有するもの、もしくはこれらが導入さ
れたものであることを特徴とする炭素、黒鉛材料。 ６）特許請求の範囲第１項記載の炭素、黒鉛材料におい
て、前記骨材は、非晶質、結晶質のいずれか少なくとも
一種であり、かつその形態が連続繊維状、短繊維状、粒
状、平板状、塊状、ブロック状、多孔体状、織布状、不
織布状の中から選ばれる一種もしくは二種以上を組合せ
て成ることを特徴とする炭素、黒鉛材料。 ７）特許請求の範囲第１項記載の炭素、黒鉛材料におい
て、前記表面処理剤及び前記添加剤は、ヒドロキシメチ
ル基、ハロメチル基のいずれか少なくとも一種の基を一
個以上有する一環または二環以上の芳香環から成る芳香
族架橋剤、もしくは前記芳香族架橋剤と酸触媒との混合
物から成る架橋能を有する組成物であることを特徴とす
る炭素、黒鉛材料。 ８）下記（ａ）〜（ｄ）のシーケンスから成ることを特
徴とする炭素、黒鉛材料の製造方法。 （ａ）少なくともその表面に水素、ハロゲン、ヒドロキ
シル基、カルボニル基、カルボキシル基、アルデヒド基
、エポキシ構造、ラクトン構造、エーテル構造、酸無水
物構造の中から選ばれる一種又は二種以上を有する骨材
の該表面を、ヒドロキシメチル基、ハロメチル基のいず
れか少なくとも一種の基を二個以上有する一環または二
環以上の芳香環から成る芳香族架橋剤を主体とする表面
処理剤によって被覆せしめた後、熱処理を行なう工程： （ｂ）主として二日以上の縮合多環芳香族化合物と、ヒ
ドロキシメチル基、ハロメチル基のいずれか少なくとも
一種の基を一個以上有する一環又は二環以上の芳香環か
ら成る芳香族架橋剤と、酸触媒とを組合せて成る熱硬化
性樹脂組成物と、前記（ａ）工程て処理した骨材とを複
合化する工程： （ｃ）前記（ｂ）工程により得られた複合物を酸化性も
しくは非酸化性雰囲気中１００〜４００℃の温度範囲に
加熱し、骨材と熱硬化性樹脂組成物とを、その界面にお
いて化学的に結合させ同時に熱硬化性樹脂組成物を硬化
させる工程： （ｄ）前記（ｃ）により得られた化合物を焼成する工程
： ９）特許請求の範囲第８項記載の炭素、黒鉛材料の製造
方法において、前記表面処理剤は、融点以上の温度に加
熱溶融させ液状とし、もしくは溶剤に溶解させ溶液とし
て使用することを特徴とする炭素、黒鉛材料の製造方法
。 １０）特許請求の範囲第８項記載の炭素、黒鉛材料の製
造方法において、前記熱硬化性樹脂組成物は、前記縮合
多環芳香族化合物と前記芳香族架橋剤と前記酸触媒との
粉末混合物、または前記粉末混合物を酸化性もしくは非
酸化性雰囲気中６０〜３００℃の温度範囲に加熱反応さ
せてなる実質的に熱可塑性を有する熱硬化性中間反応生
成物であり、これらを粉末として、加熱溶融させた液状
として、または溶剤に溶解させた溶液として使用するこ
とを特徴とする炭素、黒鉛材料の製造方法。 １１）特許請求の範囲第８項記載の炭素、黒鉛材料の製
造方法において、前記焼成は、誘導加熱によりなされる
ことを特徴とする炭素、黒鉛材料の製造方法。 １２）特許請求の範囲第８項記載の炭素、黒鉛材料の製
造方法において、前記焼成は、直接通電によりなされる
ことを特徴とする炭素、黒鉛材料の製造方法。 １３）下記（ａ）〜（ｃ）のシーケンスから成ることを
特徴とする炭素、黒鉛材料の製造方法。 （ｄ）主として二環以上の縮合多環芳香族化合物と、ヒ
ドロキシメチル基、ハロメチル基のいずれか少なくとも
一種の基を二個以上有する一環または二環以上の芳香環
から成る芳香族架橋剤と、酸触媒とを組合せて成る熱硬
化性樹脂組成物に、過剰の前記架橋剤もしくは前記架橋
剤と前記酸触媒との混合物から成る添加剤を加え、これ
に少なくともその表面に水素、ハロゲン、ヒドロキシル
基、カルボニル基、カルボキシル基、アルデヒド基、エ
ポキシ構造、ラクトン構造、エーテル構造、酸無水物構
造の中から選ばれる一種又は一種以上を有する骨材を加
えて複合化する工程： （ｂ）前記（ａ）工程により得られた複合物を酸化性も
しくは非酸化性雰囲気中１００〜４００℃の温度範囲に
加熱し、骨材と熱硬化性樹脂組成物とを、その界面にお
いて化学的に結合させ同時に熱硬化性樹脂組成物を硬化
させる工程： （ｃ）前記（ｂ）により得られた化合物を焼成する工程
： １４）特許請求の範囲第１３項記載の炭素、黒鉛材料の
製造方法において、前記添加剤は、融点以上の温度に加
熱溶融させ液状とし、もしくは溶剤に溶解させ溶液とし
て使用することを特徴とする炭素、黒鉛材料の製造方法
。 １５）特許請求の範囲第１３項記載の炭素、黒鉛材料の
製造方法において、前記熱硬化性樹脂組成物は、前記縮
合多環芳香族化合物と前記芳香族架橋剤と前記酸触媒と
の粉末混合物、または前記粉末混合物を酸化性もしくは
非酸化性雰囲気中６０〜３００℃の温度範囲に加熱反応
させてなる実質的に熱可塑性を有する熱硬化性中間反応
生成物でありこれらを粉末として、加熱溶融させた液状
として、または溶剤に溶解させた溶液として使用するこ
とを特徴とする炭素、黒鉛材料の製造方法。 １６）特許請求の範囲第１３項記載の炭素、黒鉛材料の
製造方法において、前記焼成は、誘導加熱によりなされ
ることを特徴とする炭素、黒鉛材料の製造方法。 １７）特許請求の範囲第１３項記載の炭素、黒鉛材料の
製造方法において、前記焼成は、直接通電によりなされ
ることを特徴とする炭素、黒鉛材料の製造方法。[Scope of Claims] 1) An aromatic bridge consisting mainly of a fused polycyclic aromatic compound having two or more rings and one or more aromatic rings having one or more groups of at least one of hydroxymethyl group and halomethyl group. A thermosetting resin composition formed by reacting an acid catalyst with an acid catalyst; and an aggregate having a surface functional group; A carbon or graphite material characterized by being chemically bonded via a surface treatment agent or additive and then fired. 2) In the carbon or graphite material according to claim 1, the thermosetting resin composition is a mixture of the fused polycyclic aromatic compound, the aromatic crosslinking agent, and the acid catalyst, or a mixture thereof. A carbon or graphite material characterized in that at least one selected from thermosetting intermediate reactive components is thermosetted by reaction. 3) In the carbon or graphite material according to claim 1, the fused polycyclic aromatic compound is coal-based or petroleum-based heavy oil, tar, pitch, or naphthalene, anthracene, phenanthrene, pyrene, chrysene. , naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as main skeletons, or a mixture of two or more thereof. 4) In the carbon or graphite material according to claim 1, the acid catalyst is one selected from aluminum salts, boron fluoride, phosphoric acid, organic sulfonic acids, carboxylic acids, and derivatives thereof. Carbon and graphite materials characterized by being a mixture of two or more types. 5) In the carbon and graphite material according to claim 1, the aggregate is one or more compounds selected from carbon, graphite, natural and synthetic polymers, and precursors thereof; It is a mixture and has at least one or two or more selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure on its surface. A carbon or graphite material characterized by being a carbon or graphite material, or a material into which these materials are introduced. 6) In the carbon or graphite material according to claim 1, the aggregate is at least one of amorphous and crystalline, and has a form of continuous fibers, short fibers, granules, A carbon or graphite material characterized by being made of one or a combination of two or more selected from the group consisting of a flat plate, a lump, a block, a porous body, a woven fabric, and a nonwoven fabric. 7) In the carbon or graphite material according to claim 1, the surface treatment agent and the additive are one- or two- or more-ring compounds having at least one group of at least one of a hydroxymethyl group and a halomethyl group. A carbon or graphite material characterized in that it is a composition having a crosslinking ability consisting of an aromatic crosslinking agent consisting of an aromatic ring, or a mixture of the aromatic crosslinking agent and an acid catalyst. 8) A method for producing a carbon or graphite material, characterized by comprising the following sequences (a) to (d). (a) Aggregate having one or more types selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure on at least its surface. After coating the surface with a surface treatment agent mainly consisting of an aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one of hydroxymethyl groups and halomethyl groups, Heat treatment step: (b) An aromatic compound consisting mainly of a condensed polycyclic aromatic compound of two or more days and one or two or more aromatic rings having at least one group of at least one of a hydroxymethyl group and a halomethyl group. A step of compounding a thermosetting resin composition formed by combining a crosslinking agent and an acid catalyst with the aggregate treated in step (a): (c) Composite obtained in step (b) above. is heated to a temperature range of 100 to 400°C in an oxidizing or non-oxidizing atmosphere to chemically bond the aggregate and the thermosetting resin composition at the interface and simultaneously harden the thermosetting resin composition. Step: (d) Calcining the compound obtained in the above (c): 9) In the method for producing a carbon or graphite material according to claim 8, the surface treatment agent is heated to a temperature equal to or higher than the melting point. A method for producing carbon and graphite materials, which is characterized by heating and melting them to form a liquid, or dissolving them in a solvent and using them as a solution. 10) In the method for producing a carbon or graphite material according to claim 8, the thermosetting resin composition is a powder mixture of the fused polycyclic aromatic compound, the aromatic crosslinking agent, and the acid catalyst. , or a thermosetting intermediate reaction product having substantially thermoplastic properties obtained by subjecting the powder mixture to a heating reaction in an oxidizing or non-oxidizing atmosphere at a temperature range of 60 to 300°C; A method for producing carbon and graphite materials, characterized in that they are used as a molten liquid or as a solution dissolved in a solvent. 11) The method for producing a carbon or graphite material according to claim 8, wherein the firing is performed by induction heating. 12) The method for producing a carbon or graphite material according to claim 8, wherein the firing is performed by direct energization. 13) A method for producing a carbon or graphite material, characterized by comprising the following sequences (a) to (c). (d) an aromatic crosslinking agent consisting mainly of a condensed polycyclic aromatic compound having two or more rings and one or more aromatic rings having two or more of at least one of hydroxymethyl groups and halomethyl groups; An additive consisting of an excess of the crosslinking agent or a mixture of the crosslinking agent and the acid catalyst is added to a thermosetting resin composition consisting of a combination of an acid catalyst and a hydrogen, halogen, or hydroxyl group on at least the surface thereof. , a carbonyl group, a carboxyl group, an aldehyde group, an epoxy structure, a lactone structure, an ether structure, and an acid anhydride structure. ) The composite obtained by the process is heated to a temperature range of 100 to 400°C in an oxidizing or non-oxidizing atmosphere to chemically bond the aggregate and the thermosetting resin composition at the interface, and at the same time heat Step of curing the curable resin composition: (c) Step of firing the compound obtained in the step (b): 14) In the method for producing a carbon or graphite material according to claim 13, the additive is a method for producing carbon and graphite materials, which is characterized by heating and melting them to a temperature above their melting point to form a liquid, or dissolving them in a solvent and using them as a solution. 15) In the method for producing a carbon or graphite material according to claim 13, the thermosetting resin composition is a powder mixture of the fused polycyclic aromatic compound, the aromatic crosslinking agent, and the acid catalyst. , or a thermosetting intermediate reaction product having substantially thermoplastic properties obtained by subjecting the powder mixture to a heating reaction in an oxidizing or non-oxidizing atmosphere at a temperature range of 60 to 300°C; 1. A method for producing carbon and graphite materials, characterized in that they are used in a liquid form or as a solution dissolved in a solvent. 16) The method for producing a carbon or graphite material according to claim 13, wherein the firing is performed by induction heating. 17) The method for producing a carbon or graphite material according to claim 13, wherein the firing is performed by direct energization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61034761A JPS62191469A (en) | 1986-02-19 | 1986-02-19 | Carbon, graphite material using thermosetable resin and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61034761A JPS62191469A (en) | 1986-02-19 | 1986-02-19 | Carbon, graphite material using thermosetable resin and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62191469A true JPS62191469A (en) | 1987-08-21 |
| JPH0468260B2 JPH0468260B2 (en) | 1992-10-30 |
Family
ID=12423297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61034761A Granted JPS62191469A (en) | 1986-02-19 | 1986-02-19 | Carbon, graphite material using thermosetable resin and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62191469A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005516883A (en) * | 2002-02-06 | 2005-06-09 | タッチストーン リサーチ ラボラトリー， エルティーディー． | Microwave-assisted treatment of carbon foam |
| JP2005200276A (en) * | 2004-01-16 | 2005-07-28 | Hitachi Chem Co Ltd | Method for producing graphite-amorphous carbon composite material, graphite-amorphous carbon composite material, negative electrode for battery, and battery |
| WO2015129669A1 (en) * | 2014-02-28 | 2015-09-03 | コスモ石油株式会社 | Finely pulverized petroleum coke, fired finely pulverized petroleum coke, filler for rubber composition, and rubber composition |
| JP2015178583A (en) * | 2014-02-28 | 2015-10-08 | コスモ石油株式会社 | Filler and composition containing the same |
-
1986
- 1986-02-19 JP JP61034761A patent/JPS62191469A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005516883A (en) * | 2002-02-06 | 2005-06-09 | タッチストーン リサーチ ラボラトリー， エルティーディー． | Microwave-assisted treatment of carbon foam |
| KR100979641B1 (en) * | 2002-02-06 | 2010-09-02 | 터치스톤 리서치 래버러토리 리미티드 | Microwave assisted treatment of carbon foam |
| JP2005200276A (en) * | 2004-01-16 | 2005-07-28 | Hitachi Chem Co Ltd | Method for producing graphite-amorphous carbon composite material, graphite-amorphous carbon composite material, negative electrode for battery, and battery |
| WO2015129669A1 (en) * | 2014-02-28 | 2015-09-03 | コスモ石油株式会社 | Finely pulverized petroleum coke, fired finely pulverized petroleum coke, filler for rubber composition, and rubber composition |
| JP2015178583A (en) * | 2014-02-28 | 2015-10-08 | コスモ石油株式会社 | Filler and composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0468260B2 (en) | 1992-10-30 |
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